The present invention relates to fabric care compositions, articles of manufacture and/or methods of use for treating fabrics to improve fabric appearance, especially with regards to color of fabrics, especially those that have been worn and having a faded appearance.
There is a continuous need for improved compositions, products, and methods that provide useful benefits to fabrics, especially clothing, such as maintaining and/or improving a good appearance, especially fabric color, especially for fabric that have been worn, through a simple and convenient application of a product.
Consumers commonly judge the desirability and wearability of a garment by many appearance criteria, such as, absence of color fading, absence of wrinkles, absence of soiling and staining, absence of damage such as pilling, and the like. It is preferable that these benefits are provided via simple and convenient consumer compositions, methods and products, that can be applied in the consumer""s home. These consumer compositions and products are preferably safe, and do not involve complicated and/or unsafe treatments and/or applications. Desirably they comprise treatments that are familiar to the consumers, such as spraying, soaking, adding to the wash cycle, adding to the rinse cycle, and/or adding to the drying cycle.
Many published fabric care compositions methods try to provide fabric maintenance benefits, e.g., keep fabric from, e.g., fading, wear, pilling, soiling, staining, shrinkage, and the like. However, fabric articles, such as clothing, that are worn and used will get damaged via, e.g., mechanical abrasion in use and in the laundry washing processes. The resulting worn, damaged fabric can have loosened fabric weave and pilling. Worn, damaged color fabric especially has a undesirable faded appearance. A common method that the consumer can practice to improve and/or restore the color of such worn, faded fabric is the use of fabric dyes. However, dyeing processes done at home tend to result in color bleeding in the subsequent washes that can discolor other fabrics in the same wash. Furthermore, when the fabric color is not uniform, such as when the fabric has a design with different colors and/or different tones of the same color, the use of fabric dyes is not desirable.
The present invention comprises compositions, articles of manufacture, and/or method of use that can be used to improve color fidelity, i.e., recover, restore, rejuvenate color of worn, damaged clothing upon a single application. The color benefit provided by the compositions, articles and/or methods of the present invention will endure after the treated fabric is washed at least one time, and preferably at least after the fabric is washed two times.
The present invention optionally can provide other fabric care benefits, such as abrasion resistance, wrinkle removal, pill prevention, anti-shrinkage, and fabric shape retention.
The present invention relates to fabric color care compositions, preferably aqueous and/or alcoholic fabric color care compositions, and fabric care methods for treating fabrics by direct application of said fabric color care composition to said fabrics. The present invention further relates to articles of manufacture that facilitate the use of said fabric color care compositions to restore and/or rejuvenate the color of worn, faded color fabrics, such that the color benefit can be detected after the treated fabric is washed at least one time, and more preferably at least two times. The present invention also relates to the use of selected enduring fabric color care actives and composition comprising said enduring fabric color care actives to restore and/or rejuvenate the color of worn, faded color fabrics such that the color benefit lasts at least after the treated fabric is washed and dried one time, preferably at least after the treated fabric is washed and dried two times.
The enduring fabric color care active that can provide a long lasting color restoration and/or rejuvenation benefit to worn, faded fabrics is characterized by its ability to reduce the two following properties of said fabric, namely, its reflectance and its pill number.
A preferred enduring fabric color care composition comprises an effective amount of fabric color care active preferably being selected from the group consisting of:
(A) water soluble and/or water dispersible cationic polymer; said polymer being selected from the group consisting of natural polymers, synthetic polymers, substituted materials thereof, derivatised materials thereof, and mixtures thereof;
(B) water dispersible reactive silicone, including silicones comprising amino functional groups; and
(C) mixtures thereof;
said composition additionally being essentially free of any material that would cause the treated fabric to feel unduly sticky, or xe2x80x9ctackyxe2x80x9d to the touch under usage conditions, and wherein said fabric color care active is preferably colorless at the level used, to minimize the change of hue and to improve the color fidelity.
Said composition is applied to fabric in a positive step, e.g., spraying, dipping, and/or soaking process, followed by a drying step to maximize the application and retention of the active to the surface of the fibers. Preferably the treatment is by spray and/or roller so that the active is primarily applied to the visible surface of the fabric. The present invention also preferably relates to the fabric care compositions incorporated into a spray dispenser, to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with said compositions containing fabric color care active and other optional ingredients at a level that is effective.
For some compositions, where inhalation is a concern, it is more suitable to treat fabric by dipping in such compositions.
Also, concentrated aqueous, alcoholic, or solid, preferably powder, fabric color care compositions can be used to prepare such compositions for treating worn, faded and/or damaged fabric.
The present invention also relates to a method for restoring and/or rejuvenating color of a worn, faded color fabric, wherein the color benefit can be detected after the treated fabric is washed one time, and wherein said method comprises applying an effective amount of a fabric color care active to said fabric, wherein said fabric color care active is selected from the group consisting of:
(A) water soluble and/or water dispersible cationic polymer, substituted materials thereof, derivatised materials thereof, and mixtures thereof;
(B) water dispersible reactive silicone, including amino functional silicone; and mixtures thereof; and
(C) mixtures thereof;
and wherein the color restoration and/or rejuvenation is characterized by the ability of said active to change the properties of a worn, faded black cotton (chino) twill test fabric, said changes in properties comprising:
(a) a percentage reflectance reduction xcex94R of at least about 3%; preferably at least about 5%, more preferably at least about 8%, and even more preferably at least about 10%; and
(b) a percentage pill number reduction xcex94P of at least about 10%, preferably at least about 20%, more preferably at least about 40%, and even more preferably at least about 80%.
It is especially preferred that an article of the present invention, or any container containing said composition or a concentrate used to prepare a composition of the present invention have a set of instructions associated therewith to inform the consumer that the composition can provide the color restoration benefit to worn, damaged and faded color fabric. Without knowledge of this unobvious benefit, a consumer would be highly unlikely to treat the visible surface of the fabric, especially older fabrics, and might even discard the fabric when it could be substantially restored to near-new condition.
The present invention relates to fabric color care compositions, preferably aqueous fabric color care compositions, and fabric care methods for treating fabrics by direct application of said fabric color care compositions to said fabrics. The present invention further relates to articles of manufacture that facilitate the use of said fabric color care compositions to restore and/or rejuvenate the color of worn, faded color fabrics, such that the color benefit may be detected after the treated fabric is washed at least one time, and preferably at least two times. The present invention also relates to the use of selected enduring fabric color care actives and compositions comprising said enduring fabric color care actives to restore and/or rejuvenate the color of worn, faded color fabrics such that the color benefit lasts at least after the treated fabric is washed one time, preferably at least after the treated fabric is washed two times.
The color restoration and/or rejuvenation benefit to the worn, faded fabric is characterized by the ability of the fabric color care active to change the two following properties of worn, faded black cotton (chino) twill test fabric (as defined hereinbelow), said changes in properties comprising:
(A) a percentage reflectance reduction xcex94R of at least about 3%, preferably at least about 5%, more preferably at least about 8%, and even more preferably at least about 10%; and
(B) a percentage pill number reduction xcex94P of at least about 10%, preferably at least about 20%, more preferably at least about 40%, and even more preferably at least about 80%;
with xcex94R and xcex94P being measured on treated fabric that is washed and dried at least one time, preferably at least two times, as compared to the untreated worn, faded black cotton fabric that are washed and dried similarly.
The preferred fabric color care composition of the present invention comprises:
(A) an effective amount of fabric color care active for restoring and/or rejuvenating the color of worn, faded color fabric, said fabric color care active is preferably selected from the group consisting of water soluble and/or water dispersible cationic polymer, substituted materials thereof, derivatised materials thereof, and mixtures thereof; water dispersible reactive silicone, including silicones comprising amino functional groups; and mixtures thereof;
(B) optionally, an effective amount to provide olfactory effects of perfume;
(C) optionally, to reduce surface tension, and/or to improve performance and formulatability, an effective amount of surfactant;
(D) optionally, an effective amount to absorb malodor, of odor control agent;
(E) optionally, an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active;
(F) optionally, an effective amount to provide improved antimicrobial action of aminocarboxylate chelator;
(G) optionally, an effective amount of antimicrobial preservative; and
(H) optionally, an aqueous and/or alcoholic carrier;
said composition additionally being essentially free of any material that would cause the treated fabric to feel unduly sticky, or xe2x80x9ctackyxe2x80x9d to the touch under usage conditions, and wherein said fabric color care active is preferably colorless at the level used, to minimize the change of hue and to improve the color fidelity.
The present invention also relates to methods and articles of manufactures for treating fabrics using compositions comprising preferred fabric-substantive and/or fabric reactive fabric color care actives to provide a more durable color restoration and/or color rejuvenation benefit that lasts at least after one washing cycle, preferably at least after two or more washing cycles.
The present invention also relates to branded articles of manufacture comprising the fabric color care composition of the present invention whose value to the consumer has been improved by marketing it in association with the information that durable color restoration and/or rejuvenation benefit to a fabric can be obtained and/or achieved by applying at least an effective amount of said fabric care composition to said fabric. By xe2x80x9cbrandedxe2x80x9d it is meant that the article can be identified as one that has been associated with the indicated benefit, thus, including trademarks, tradenames, and any other identifying characteristic such as trade dress, color, odor, sound, etc. that the consumer can use to associate the particular article with a specific benefit that has been taught. This enables the consumer to know that the benefit can be achieved, even when the product is separated from the original information, e.g., when the product has had part of the instructions destroyed, or when the article is marketed without the information about the specific benefit.
The present invention relates to the application of an effective amount of an enduring fabric color care active and/or fabric color care composition to fabric to modify the following fabric properties, namely, a reduction of reflectance, and a reduction of the microfibril number to reduce the loss of fabric color and/or to recover fabric color. It has not previously been recognized that the use of the above compositions can provide good color restoration and/or recovery.
The present invention can optionally provide other fabric care benefits, such as, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric soiling reduction, fabric soil release, wrinkle resistance, wrinkle reduction, anti-shrinkage, fabric shape retention, and mixtures thereof.
Methods for Determining the Observed Color Restoration Benefit
The utility of a fabric color care active can be determined by the following simple screening test procedures. The desired fabric properties are determined using worn black chino (cotton) twill test fabric that is available from TESTFABRICS, Inc., West Pittston, Pa. Worn black cotton twill test fabric is obtained by treating new fabric through eight treatment cycles, each washing/drying treatment cycle comprises of one washing/rinsing cycle with the AATCC powder detergent, all cycles using about 90xc2x0 F. water in a Kenmore automatic clothes washer Model 110, followed by a drying cycle in a Kenmore automatic electric tumble dryer Model 110. The resulting test fabric is visibly worn and faded. Some worn fabric samples are retained for use as control worn fabrics. Other worn fabric samples are treated using the method of the present invention. The treated and untreated fabric samples are washed and dried one more time in the washer with hand wash setting, with detergent and with cold water. After drying, the rewashed control and therewashed treated fabrics are examined visually and their properties are determined by the following two test procedures.
Reflectance
The reduction of reflectance of a fabric is determined using the optical measurement from the LabScan(copyright) XE instrument from Hunter Associates Laboratory, Inc, Reston, Va. The LabScan(copyright) XE is a full-scanning spectrophotometer with a wavelength range from 400 to 700 nanometer. The sample is illuminated by a xenon flash lamp and reflected light is collected by a 15-station fiber optic ring. For reflectance measurements, the diameter of opening in port is 50 mm. The illumination angle is 0xc2x0 (normal) to the specimen. The viewing angle is 45xc2x0 from normal via fiber optic ring.
The reflectance of the whole range of wavelength from about 420 nm to about 620 nm is measured for the black cotton twill test fabrics. For each wavelength at increments of about 10 nm, the reflectance of the treated fabric (Rt) and that of the worn, untreated fabric (Ru) are measured. The percentage reduction of the reflectance for each wavelength is
xcex94R=100xc3x97{(xcexa3Ruxe2x88x92xcexa3Rt)/xcexa3Ru}%
For a noticeable improvement and/or restoration of fabric color, xcex94R should be a positive number and having a value of at least about 3%, preferably at least about 5%, more preferably at least about 8%, and even more preferably at least about 10%.
Microfibril Number
An image analysis system is used to estimate the number of pills on the untreated and treated black cotton twill fabrics that are used to define the observed color restoration benefit. The general setup and procedure are described in xe2x80x9cEfforts to Control Pilling in Wool/Cotton Fabricsxe2x80x9d, Jeanette M. Cardamone, Textile Chemist and Colorist, 31, 27-31 (1999), incorporated herein by reference. The image analysis system utilizes a light booth with a circular fluorescent light bulb. The bulb is just above the plane of the fabric. The fabric is put into the light booth via a drawer. To remove any wrinkle the fabric is held own at the edges by a Plexiglas clamp (imagine a Plexiglas book with a hole in the cover here the fabric shows through). The pills rise above the fabric and reflect light to the monochrome camera mounted above. The camera and video frame grabber are adjusted so that the pills show up as bright features against the plane of the fabric that shows up as a dark background. The image is thresholded, and the bright blobs (pills) are counted and sized. The image analysis is done using a custom macro written in the OPTIMAS image analysis software package, available at the Meyer Instruments, Inc., Houston, Tex. The xe2x80x9cpill numberxe2x80x9d (Pt) for the treated black cotton twill fabric and that of the worn, untreated fabric (Pu) are determined. The percentage reduction of the pill number xcex94P is
xcex94P=100xc3x97(Puxe2x88x92Pt)/Pu%
It is found that for an appreciable color restoration benefit to be provided by a fabric color care composition, xcex94P should be a positive number and have a value of at least about 10%, preferably at least by about 20%, more preferably at least about 40%, and even more preferably at least about 80%. A preferred enduring fabric color care active of the present invention comprises of water dispersible, preferably water soluble cationic polymers which contain quaternized nitrogen groups and/or nitrogen groups having strong cationic charges which are formed in situ under the conditions of usage. They can be natural, or synthetic polymers, substituted polymer materials thereof, derivatised polymer materials thereof, and mixtures thereof. A particularly preferred class of polymer comprises water dispersible reactive silicones, including silicones comprising amino functional groups.
Cationic Derivatives of Natural Polymers
Preferred enduring fabric color care actives of the present invention include water soluble and/or water dispersible cationic derivatives of natural polymers which are derived from natural sources, preferably polysaccharides, oligosaccharides, proteins; substituted versions of said polymers; and mixtures thereof. The preferred polymer is preferably colorless under usage conditions, to minimize the change of hue and to improve the color fidelity.
Preferred active of this class is selected from the group consisting of cationic derivatives of polysaccharides; proteins; glycoproteins; glycolipids; substituted versions of said polymers; and mixtures thereof.
Synthetic Polymers
Another preferred enduring fabric color care active of the present invention include water soluble and/or water dispersible cationic synthetic polymers. The preferred polymer is preferably colorless under usage conditions, to minimize the change of hue and to improve the color fidelity. Cationic enduring fabric color care synthetic polymer includes: homopolymer and copolymer containing hydrophilic monomers and/or hydrophobic monomers.
Specially preferred enduring fabric color care synthetic polymer includes: water dispersible silicones comprising amino functional groups, including reactive, curable silicones comprising amino functional groups, and their derivatives. A class of silicone derivatives that is particularly preferred in the present invention is cationic silicones containing polyalkylene oxy groups, including reactive, curable silicones comprising cationic aminofunctional groups and polyalkyleneoxy groups. Also preferred are reactive, curable silicones comprising polyalkyleneoxy groups, but not cationic amino functional groups. The polyalkyleneoxy groups hereinabove comprise at least some ethyleneoxy units.
A preferred fabric color care composition for treating worn and/or faded colored fabrics comprises an effective amount of said fabric color care active, and optionally, at least one adjunct ingredient selected from the group consisting of perfume, odor control agent, antimicrobial active and/or preservative, surfactant, optical brightener, antioxidant, chelating agent including aminocarboxylate chelating agent, antistatic agent, dye transfer inhibiting agent, fabric softening active, and/or static control agent.
Enzymes are not preferred in the compositions of the present invention, especially in the spray compositions, because aerosolized particles containing enzymes often constitute a health hazard. Cationic dye fixing agents are also not preferred.
The composition is typically applied to fabric via a positive step, e.g., spraying, dipping, soaking and/or direct padding process, e.g., impregnating the fabric using rollers, brushes, foam, printing, to treat substantially all of the visible surface followed by a drying step, including the process comprising a step of treating or spraying the fabric with the fabric care composition either outside or inside an automatic clothes dryer followed by, or concurrently with, the drying step in said clothes dryer. The application can be done industrially by large scale processes on textiles and/or finished garments and clothing, or, preferably, in the consumer""s home through the use of commercial consumer products comprising enduring fabric color care actives.
The fabric color care spray composition contains enduring fabric color care active at a level of from about 0.01% to about 20%, typically from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, even more preferably from about 0.3% to about 2%, by weight of the usage composition.
The present invention also relates to concentrated liquid or solid fabric color care compositions, which are diluted to form compositions with the usage concentrations, as given hereinabove, for use in the xe2x80x9cusage conditionsxe2x80x9d. Concentrated compositions comprise a higher level of enduring fabric color care active, typically from about 1% to about 99%, preferably from about 2% to about 65%, more preferably from about 3% to about 25%, by weight of the concentrated fabric color care composition. Concentrated compositions are used in order to provide a less expensive product per use. When a concentrated product is used, i.e., when the fabric color care active is from about 1% to about 99%, by weight of the concentrated composition, it is preferable to dilute the composition before treating fabric. Preferably, the concentrated fabric care is diluted with about 50% to about 10,000%, more preferably from about 50% to about 8,000%, and even more preferably from about 50% to about 5,000%, by weight of the composition, of water.
The present invention also relates to concentrated liquid or solid fabric color care compositions wherein the enduring color care actives are reactive and/or hydrolyzable, and preferably need to be isolated from any water that is present in the compositions, to improve the storage stability of the product. Concentrated compositions comprise a higher level of reactive enduring fabric color care active, typically from about 1% to about 99%, preferably from about 2% to about 65%, more preferably from about 3% to about 25%, by weight of the concentrated fabric color care composition. In use, the product is diluted to form compositions with the usage concentrations, as given hereinabove, for immediate use in the xe2x80x9cusage conditionsxe2x80x9d. Alternatively, a relatively concentrated composition can be applied directly on wet fabrics so that the enduring color care actives can be diluted in situ on the wet fabrics, e.g., fabrics that have washed without drying before applying a composition of the present invention. When applied directly to wet fabric, the fabrics color care compositions of the present invention contain said fabric color care active at a level from about 0.01% to about 25%, preferably from about 0.1% to about 10%, more preferably from about 0.2% to about 5%, and even more preferably from about 0.3% to about 3% by weight of the composition.
The present invention preferably comprises articles of manufacture that include such fabric color care compositions. Thus the present invention relates to the compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric surfaces with said fabric care compositions containing a fabric color care active and other optional ingredients at a level that is effective when dried on the surfaces. The spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the fabric color care composition. For a non-manually operated sprayer, preferably battery powered for safety reasons in the home, the container is preferably the one sold in the store containing the fabric color care composition that is applied to the fabric, adapted to be used with the particular sprayer. The invention also comprises containers that are adapted for use with spray dispensers.
The present invention also relates to an article of manufacture comprising fabric care compositions at usage concentrations to facilitate treatment of fabric surfaces with said fabric care compositions containing a fabric color care active and other optional ingredients at a level that is effective, said composition is applied to fabric in a positive step, e.g., dipping, soaking, padding process, or by a roller, followed by a drying step to maximize the application and retention of the active to the surface of the fibers. More preferably, the article of manufacture comprises concentrated fabric care compositions to be diluted to usage concentrations in use.
Preferably, the articles of manufacture are in association with a set of instructions that direct the consumer how to use the composition to treat fabrics correctly, to obtain the desirable fabric care results, viz, color renewal, and preferably, other additional fabric care benefits, such as wrinkle removal, wrinkle resistance, fiber strengthening/anti-wear, pill prevention, anti-shrinkage, soiling prevention and/or reduction, and/or fabric shape retention, including, e.g., the manner and/or amount of composition to used, and the preferred ways of checking for completeness of application, stretching and/or smoothing of the fabrics. Ironing and/or smoothing can help distribute the active over the surface and partially compensate for incomplete distribution. As used herein, the phrase xe2x80x9cin association withxe2x80x9d means the instructions that are either directly printed on the container itself or presented in a different manner including, but not limited to, a brochure, print advertisement, electronic advertisement, and/or verbal communication, so as to communicate the set of instructions to a consumer of the article of manufacture. It is important that the instructions be simple and clear. The use of pictures and/or icons within the instructions may be desirable.
Enduring Fabric Color Care Active
The fabric color care spray composition contains an enduring fabric color care active at a level of from about 0.01% to about 20%, typically from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, even more preferably from about 0.3% to about 2%, by weight of the usage composition. The present invention also relates to concentrated liquid or solid fabric color care compositions, which are diluted to form compositions with usage concentrations, as given hereinabove, for use under xe2x80x9cusage conditionsxe2x80x9d. Concentrated compositions comprise a higher level of enduring fabric color care active, typically from about 1% to about 99%, preferably from about 2% to about 65%, more preferably from about 3% to about 25%, by weight of the concentrated fabric color care composition. Concentrated compositions are used in order to provide a less expensive product per use. When a concentrated product is used, i.e., when the enduring fabric color care active is from about 1% to about 99%, by weight of the concentrated composition, it is preferable to dilute the composition before treating fabric. Preferably, the concentrated fabric care is diluted with about 50% to about 10,000%, more preferably from about 50% to about 8,000%, and even more preferably from about 50% to about 5,000%, by weight of the composition, of water.
Preferred enduring color care active includes cationic and/or reactive polymers to provide color restoration to worn, faded fabric. Said polymers comprise cationic functional groups, and/or reactive groups that can further condense to form higher molecular weight polymers. Useful cationic polymers include natural polymers, derivatives thereof, synthetic polymers, and mixtures thereof. These polymers are preferably colorless, to minimize the change of hue and to improve the color fidelity.
Water Soluble and Water Dispersible Derivatives of Natural Polymers
An enduring fabric color care active useful in the present invention comprises water soluble and/or water dispersible cationic polymers derived from natural sources, preferably selected from the group consisting of polysaccharides; proteins; glycoproteins; glycolipids; substituted versions thereof; derivatised versions thereof; and mixtures thereof. The preferred polymer is colorless at the effective concentrations, to minimize the change of hue and to improve the color fidelity.
Water Soluble/Dispersible Polysaccharides
Preferably, said polysaccharides have a molecular weight of from about 1,000 to about 2,000,000, more preferably from about 5,000 to about 1,000,000, and even more preferably from about 10,000 to about 300,000. Nonlimiting examples of water soluble/dispersible polysaccharides to form cationic derivatives useful in the present invention includes the following:
(i) Heteropolysaccharides derived from the bark, seeds, roots and leaves of plants, which are divided into two distinct groups, namely, acidic polysaccharides described as gums, mucilages and pectins, and the neutral polysaccharides known as hemicelluloses,
(ii) Algal polysaccharides including food-reserve polysaccharides (e.g., laminaran), structural polysaccharides (e.g., D-xylans, D-mannans), sulphated polysaccharides that are isolated from algae (e.g., carrageenan, agar), other algal mucilages which have similar properties and usually contain L-rhamnose, D-xylose, D-glucuronic acid, D- and L-galactose and D-mannose,
(iii) Microbial polysaccharides, such as teichoic acids, cell wall peptidoglycans (mureins), extracellular polysaccharides, gram-positive bacterial capsular polysaccharides and gram-negative bacterial capsular polysaccharides.
(iv) Lipopolysaecharides,
(v) Fungal polysaccharides, and
(vi) Animal polysaccharides (e.g., glycogen, chitosan).
A preferred polysaccharide is hemicelluloses selected from the group consisting of L-arabino-D-galactan; D-gluco-D-mannan, D-galacto-D-gluco-D-mannan, partly acetylated (4-O-methyl-D-glucurono)-D-xylan, L-arabino-(4-O-methyl-D-glucurono)-D-xylan; substituted versions thereof; derivatised versions thereof; and mixtures thereof; and more preferably, arabinogalactan. Arabinogalactans are long, densely branched high-molecular weight polysaccharides. Arabinogalactan that is useful in the composition of the present invention has a molecular weight range of from about 5,000 to about 500,000, preferably from about 6,000 to about 250,000, more preferably from about 10,000 to about 150,000. These polysaccharides are highly branched, consisting of a galactan backbone with side-chains of galactose and arabinose units. Most commercial arabinogalactan is produced from western larch, through a counter-current extraction process. Larch arabinogalactan is water soluble and is composed of arabinose and galactose units in about a 1:6 ratio, with a trace of uronic acid. The molecular weights of the preferred fractions of larch arabinogalactan include one fraction in the range of from about 14,000 to about 22,000, mainly from about 16,000 to about 21,000, and the other in the range of from about 60,000 to about 500,000, mainly from about 80,000 to about 120,000. The fraction that has the average molecular weight of from about 16,000 to about 20,000 is highly preferred for use in direct applications to fabric, such as in spray-on products.
Other cationic polysaccharides such as chitosan are also useful in the present invention. Chitosan is poly (D-glucosamine) and is derived from chitin, a linear polysaccharide consisting of N-acetyl-D-glucosamine. Chitin is widely distributed in nature, e.g., in the shells of crustaceans and insects, and in the cell wall of bacteria. Chitosan is prepared by the deacetylation of chitin. Chemically, chitosan is very similar to cellulose, differing only in the fact that chitosan has an amino group instead of hydroxyl group at C-2. In spite of the similarity in structure with cellulose, the chemical and physical properties of chitosan are significantly different from those of cellulose. Preferred chitosan materials for use in the present invention are ethoxylated chitosans wherein polyethylene glycol moieties are grafted to chitosan to improve its solubility.
Water Soluble/Dispersible Proteins
Nonlimiting examples of water soluble/dispersible proteins useful in the present invention includes: globular proteins, such as albumins, globulins, protamines, histones, prolamines and glutelins; low levels of fibrous proteins, such as elastin, fibroin and sericin; and conjugated proteins with one or more non-protein moieties such as carbohydrates, lipids, and phosphate residues. The proteins useful herein preferably do not include enzymes, specially in the spray compositions, because aerosolized particles containing enzymes often constitute a health hazard.
Nonlimiting examples of such enduring fabric color care actives include cationic arabinogalactan, cationic functional celluloses, and polyethoxylated chitosan. An example of cationic arabinogalactans is LaraCare(copyright) C300, a hydroxypropyl trimethyl ammonium chloride derivative of arabinogalactan, having xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94N+(CH3)3Clxe2x88x92 pendant groups, available from Larex, Inc., White Bear Lake, Minn. Examples of water soluble quaternary cellulose derivatives are Celquat(copyright) polymers, available from National Starch and Chemical Company, Bridgewater, N.J. Examples of Celquat polymers include Celquat H-100 and Celquat L-200 which are of Polyquaternium-4 type, that is polymeric quaternary ammonium salt of hydroxyethylcellulose and diallyldimethyl ammonium chloride, and Celquat SC230M and Celquat SC240C which are of Polyquaternium-10 type, that is polymeric quaternary ammonium salt of hydroxyethylcellulose reacted with a trimethyl ammonium substituted epoxide. Celquat H-100 has a percentage quaternized nitrogen of about 1.0 and a molecular weight of about 1,400,000; Celquat L-200 has a percentage quaternized nitrogen of about 2.0 and a molecular weight of about 300,000; Celquat SC230M has a percentage quaternized nitrogen of about 1.9 and a molecular weight of about 1,700,000; and Celquat SC240C has a percentage quaternized nitrogen of about 1.8 and a molecular weight of about, 1,100,000. An example of silk proteins is Aquapro(copyright) QW, available from Mid West Grain Products. Aqua Pro II QW is a quaternized hydrolyzed wheat protein (stearyldimonium hydroxypropyl hydrolyzed wheat protein) provided in its liquid form.
Water Soluble and Water Dispersible Cationic Synthetic Polymers
Another preferred enduring fabric color care active of the present invention includes water soluble and/or water dispersible cationic synthetic polymers. The preferred polymer is colorless at the effective concentrations, to minimize the change of hue and to improve the color fidelity. Cationic enduring fabric color care synthetic polymers includes homopolymers and copolymers comprising hydrophilic monomers and/or hydrophobic monomers. Nonlimiting examples of enduring fabric color care synthetic polymeric actives include aminofunctional silicones, reactive, curable silicones, ethoxylated polyamines, and mixtures thereof. A class of silicone derivatives that is particularly preferred in the present invention is cationic silicones containing polyalkyleneoxy groups, including reactive, curable silicones comprising cationic aminofunctional groups and polyalkyleneoxy groups. Also useful are reactive, curable silicones comprising polyalkyleneoxy groups, but not cationic amino functional groups. The polyalkyleneoxy groups hereinabove comprise at least some ethyleneoxy units. Preferably aminofunctional silicones containing ethoxylated moieties. For reactive, curable silicones comprising polyalkyleneoxy groups, the polyalkyleneoxy groups are preferably capped with C1-6alkyl groups and/or other nonreactive groups.
Silicones
Preferred enduring fabric color care active comprises cationic aminofunctional silicones; reactive, curable silicones and derivatives thereof; and mixtures thereof.
Cationic Aminofunctional Silicones. Cationic aminofunctional silicones comprise cationic xe2x80x94Xxe2x80x94E groups, with each X being a hydrocarbon or oxygenated hydrocarbon linking group, preferably being selected from the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof; and each E being a cationic nitrogen functional group, preferably being selected from the group consisting of amino group and quaternary ammonium derivatives thereof; cyclic amino group and quaternary ammonium derivatives thereof; imidazole group and imidazolium derivatives thereof; imidazoline group and imidazolinium derivatives thereof; and mixtures thereof. Each cationic functional XE group can be a pendant group, a terminal group situated at the ends of the silicone polymer backbone, an internal group incorporated as part of the silicone polymer backbone chain, and mixtures thereof. Aminofunctional silicones, optionally, but preferably, comprise one or more polyalkyleneoxy groups comprising at least some ethyleneoxy units, wherein each polyalkyleneoxy group can be a pendant group, a terminal group situated at the ends of the silicone polymer backbone, an internal group incorporated as part of the silicone polymer backbone chain, and mixtures thereof. When polyalkyleneoxy groups are present as terminal and/or pendant groups, each cationic functional XE group can also be situated at the end of said polyalkeneoxy groups.
Suitable cationic aminofunctional silicones of the current invention conform to the following general structure I:
(R1)aR3-aSixe2x80x94(xe2x80x94Oxe2x80x94SiR2)mxe2x80x94(xe2x80x94Oxe2x80x94SiRB)pxe2x80x94(xe2x80x94Oxe2x80x94SiRD)qxe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]rxe2x80x94Oxe2x80x94Si(R1)bR3-bxe2x80x83xe2x80x83(I)
wherein:
each R group is the same or different and is preferably an alkyl, aryl, and mixtures thereof, more preferably, each R is methyl, ethyl, propyl, butyl, or phenyl group, most preferably R is methyl;
each cationic B group is an xe2x80x94Xxe2x80x94E group with each X being a hydrocarbon or oxygenated hydrocarbon linking group, preferably being selected from the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof; and each E being a cationic nitrogen functional group. preferably being selected from the group consisting of amino group and quaternary ammonium derivatives thereof; cyclic amino group and quaternary ammonium derivatives thereof; imidazole group and imidazolium derivatives thereof; imidazoline group and imidazolinium derivatives thereof; polycationic group, and mixtures thereof;
each optional, but preferred D group is a poly(ethyleneoxy/propyleneoxy) group having the general structure:
xe2x80x94Zxe2x80x94O(C2H4O)c(C3H6O)dR3
xe2x80x83wherein each Z is a linking group, preferably selected from the group consisting of hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, phenylene-CH2CH2xe2x80x94 and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94; aminohydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group; and mixtures thereof; each R3 group is the same or different and being preferably selected from the group consisting of hydrogen, R, cationic nitrogen functional E group, xe2x80x94CH2CH(R)OH, xe2x80x94CH2C(R)2OH, xe2x80x94CH2CH(OH)CH2OR, xe2x80x94CH2CH(OH)CH2(OCH2CH2)eOR, tetrahydropyranyl, xe2x80x94CH(R)OR, C(O)H, and/or xe2x80x94C(O)R group, more preferably R3 group is an R group, with R being more preferably selected from methyl and/or ethyl group; each c is at least about 2, preferably at least about 5, more preferably at least about 11, and even more preferably at least about 21, total c (for all polyalkyleneoxy side groups) has a value of from about 4 to about 2500, preferably from about 6 to about 1000, more preferably from about 11 to about 800, and even more preferably from about 21 to about 500; total d is from 0 to about 1000, preferably from 0 to about 300; more preferably from 0 to about 100, and even more preferably d is 0; preferably total c is equal or larger than total d; total c+d has a value of from about 4 to about 2500, preferably from about 8 to about 800, and more preferably from about 15 to about 500; and each e is from 1 to about 20, preferably 1 or 2;
each optional G is xe2x80x94O(C2H4O)v(C3H6O)wxe2x80x94; each J is selected from X and xe2x80x94CH2CH(OH)CH2xe2x80x94; each optional E is a cationic group defined as hereinabove; each v is from 0 to about 200, preferably from about 5 to about 150, more preferably from about 11 to about 120, and even more preferably from about 21 to about 100; each w is from 0 to about 50 and preferably v is equal or larger than w; each g and k is from 0 to about 10, preferably from 0 to about 6, more preferably from about 1 to about 3, and even more preferably from about 1 to about 2; j is g+kxe2x88x921, within the segment designated as (G)gxe2x80x94(J)jxe2x80x94(E)k, the units can be arranged in any order, providing that no Oxe2x80x94O bonds and/or Nxe2x80x94N are formed;
each R1 group is the same or different and is preferably selected from the group consisting of R, B, and/or D group;
each a and/or b is an integer from 0 to 3, preferably 2, more preferably 1;
m is from about 5 to about 1600, preferably from about 6 to about 800, more preferably from about 8 to about 400, and even more preferably from about 10 to about 200;
a, and b, p, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and xe2x80x94Oxe2x80x94Si(R1)bR3-b are selected such that the silicone polymer comprises at least one cationic group in the form of an Sixe2x80x94B group; with typically the p to (m+p) ratio ranges from 0 to about 1:2, preferably from about 1:200 to about 1:3, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:4; and
a, and b, q, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3-b are selected such that the silicone polymer optionally comprises at least one poly(ethyleneoxy/propyleneoxy) Sixe2x80x94D group; and preferably at least about two Sixe2x80x94D groups; with typically the q to (m+p+q) ratio ranges from about 1:1000 to about 1:3, preferably from about 1:200 to about 1:4, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:5;
r is from 0 to about 100, preferably r is 0; when r is not 0 it is preferably from 1 to about 20, more preferably from 1 to about 10, with r being 0 when neither a polyalkyleneoxy group nor a cationic group is part of the polymer backbone; when one or more polyalkyleneoxy groups and/or cationic groups are part of the polymer backbone, the r to (m+p) ratio ranges typically from about 1:1000 to about 1:2, preferably from about 1:500 to about 1:4, more preferably from 1:200 to about 1:8, and even more preferably from about 1:100 to about 1:20;
wherein said silicone polymer can be linear, branched, and/or cyclic, preferably linear or branched, and more preferably linear; and wherein different xe2x80x94Oxe2x80x94SiR2xe2x80x94, xe2x80x94xe2x80x94Oxe2x80x94SiRBxe2x80x94, xe2x80x94Oxe2x80x94SiRDxe2x80x94, and xe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]xe2x80x94 groups can be distributed randomly in the silicone backbone and/or organized as block copolymers of different degrees.
A nonlimiting example of aminofunctional silicone polymers conforms with the formula:
(CH3)3Sixe2x80x94[Oxe2x80x94Si(CH3)2]nxe2x80x94{OSi(CH3)[(CH2)3xe2x80x94NHxe2x80x94(CH2)2]}mxe2x80x94OSi(CH3)3
wherein the sum of n+m is a number from 2 to about 1,000.
Nonlimiting examples of aminofunctional silicone polymers comprising optional polyalkyleneoxy groups include those disclosed in U.S. Pat. No. 5,098,979, issued Mar. 24, 1992 to O""Lenick disclosing some silicones with cationic capped polyalkyleneoxy pendant groups, and U.S. Pat. No. 5,196,499, issued Mar. 23, 1993 to O""Lenick disclosing some silicones with cationic capped polyalkyleneoxy terminal groups, said patents are incorporated herein by reference.
Reactive, Curable Silicones.
Reactive, curable silicone polymers comprise one or more reactive Si functional groups including Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR and/or Sixe2x80x94OCOR groups, wherein R is typically a low molecular weight alkyl group. Each reactive Si bearing a reactive functional group can be a terminal group, a pendant group, part of the silicone backbone, and mixtures thereof.
The reactive, curable silicones of the present invention conform to the following general structure II:
(R1)aR3-aSixe2x80x94(xe2x80x94Oxe2x80x94SiR2)mxe2x80x94(xe2x80x94Oxe2x80x94SiRA)n(xe2x80x94Oxe2x80x94SiRB)pxe2x80x94(xe2x80x94Oxe2x80x94SiRD)q[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]rxe2x80x94Oxe2x80x94Si(R1)bR3-bxe2x80x83xe2x80x83(II)
wherein:
each R group is the same or different and is preferably an alkyl, aryl, and mixtures thereof, more preferably, each R is methyl, ethyl, propyl, butyl, or phenyl group, most preferably R is methyl;
each A of the Si reactive functional group is the same or different and is preferably selected from the group consisting of hydrogen, xe2x80x94OH, xe2x80x94OR, xe2x80x94OCOCH3, xe2x80x94CH2CH2Si(OR)3, xe2x80x94CH2CH2Si(OR)2R, xe2x80x94CH2CH2Si(OR)R2, and mixtures thereof.
each optional, but preferred cationic B group is an xe2x80x94Xxe2x80x94E group with each X being a hydrocarbon or oxygenated hydrocarbon linking group, preferably being selected from the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof; and each E being a cationic nitrogen functional group, preferably being selected from the group consisting of amino group and quaternary ammonium derivatives thereof; cyclic amino group and quaternary ammonium derivatives thereof, imidazole group and imidazolium derivatives thereof; imidazoline group and imidazolinium derivatives thereof, polycationic group; and mixtures thereof,
each optional, but preferred D group is a poly(ethyleneoxy/propyleneoxy) group having the general structure:
xe2x80x94Zxe2x80x94O(C2H4O)c(C3H6O)dR3
xe2x80x83wherein each Z is a linking group, preferably selected from the group consisting of hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94 and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94; aminohydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group and xe2x80x94CH2CH(CH3)CH2xe2x80x94N less than  group; and mixtures thereof; each R3 group is the same or different and being preferably selected from the group consisting of hydrogen, R, JE, xe2x80x94CH2CH(R)OH, xe2x80x94CH2C(R)2OH, xe2x80x94CH2CH(OH)CH2OR, xe2x80x94CH2CH(OH)CH2(OCH2CH2)eOR, tetrahydropyranyl, xe2x80x94CH(R)OR, C(O)H, and/or xe2x80x94C(O)R group, more preferably R3 group is an R group, with R being more preferably selected from methyl and/or ethyl group; each c is at least 2, preferably at least about 5, more preferably at least about 11, even more preferably at least about 21, total c (for all polyalkyleneoxy side groups) has a value of from about 4 to about 2500, preferably from about 6 to about 1000, more preferably from about 11 to about 800, and even more preferably from about 21 to about 500; total d is from 0 to about 1000, preferably from 0 to about 300; more preferably from 0 to about 100, and even more preferably d is 0; total c is preferably equal or larger than total d; total c+d has a value of from about 4 to about 2500, preferably from about 8 to about 800, and more preferably from about 15 to about 500; and each e is from 1 to about 20, preferably 1 or 2;
each optional G is xe2x80x94O(C2H4O)v(C3H6O)wxe2x80x94; each J is selected from X and xe2x80x94CH2CH(OH)CH2xe2x80x94; each optional E is a cationic group defined as hereinabove; each v is from 0 to about 200, preferably from about 5 to about 150, more preferably from about 11 to about 120, and even more preferably from about 20 to about 100; each w is from 0 to about 50 and preferably v is equal or larger than w; each g and k is from 0 to about 10, preferably from 0 to about 6, more preferably from about 1 to about 3, and even more preferably from about 1 to about 2; j is g+kxe2x88x921, providing that no Oxe2x80x94O bonds are formed;
each R1 group is the same or different and is preferably selected from the group consisting of R, A, B, and/or D group;
each a and/or b is an integer from 0 to 3, preferably 2, more preferably 1;
m is from about 5 to about 1600, preferably from about 6 to about 800, more preferably from about 8 to about 400, and even more preferably from about 10 to about 200;
n, a, and b, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3-b are selected such that the silicone polymer comprises at least one reactive Si functional group in the form of an Sixe2x80x94A group, preferably Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR, Sixe2x80x94OCOR, and mixtures thereof, with R preferably a methyl group; and more preferably the silicone molecule comprises at least about two reactive Si functional groups; with typically the n to (m+n) ratio (and the n to (m+n+p) ratio when p is not 0), ranges from 0 to about 1:2, preferably from about 1:1500 to about 1:3, more preferably from about 1:400 to about 1:4, and even more preferably from about 1:100 to about 1:4;
p, a, and b, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3-b are selected such that the silicone polymer optionally comprises at least one cationic group in the form of an Sixe2x80x94B group; with typically the p to (m+n+p) ratio ranges from 0 to about 1:2, preferably from about 1:200 to about 1:3, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:4; and
q, a, and b, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3-b are selected such that the silicone polymer optionally comprises at least one poly(ethyleneoxy/propyleneoxy) Sixe2x80x94D group; and preferably at least about two Sixe2x80x94D groups; with typically the q to (m+n+p) ratio ranges from about 1:1000 to about 1:3, preferably from about 1:200 to about 1:4, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:5;
r is from 0 to about 100, preferably from 1 to about 20, more preferably from 1 to about 10, with r being 0 when neither a polyalkyleneoxy group nor a cationic group is part of the polymer backbone; when one or more polyalkyleneoxy groups and/or cationic groups are part of the polymer backbone, the r to (m+n+p) ratio ranges typically from about 1:1000 to about 1:2, preferably from about 1:500 to about 1:4, more preferably from 1:200 to about 1:8, and even more preferably from about 1:100 to about 1:20;
wherein said silicone polymer can be linear, branched, and/or cyclic, preferably linear or branched, and more preferably linear; and wherein different xe2x80x94Oxe2x80x94SiR2xe2x80x94, xe2x80x94Oxe2x80x94SiRAxe2x80x94, xe2x80x94Oxe2x80x94SiRBxe2x80x94, xe2x80x94Oxe2x80x94SiRDxe2x80x94, and xe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]xe2x80x94 groups can be distributed randomly in the silicone backbone and/or organized as block copolymers of different degrees.
Simple reactive silicones that do not have amino functional groups and polyalkyleneoxy groups are also suitable for use in the composition of the present invention. Nonlimiting examples of this class include polyalkyl and/or phenyl silicone fluids with the following structure:
Axe2x80x94Si(R2)xe2x80x94Oxe2x80x94[Si(R2)xe2x80x94Oxe2x80x94]qxe2x80x94Si(R2)xe2x80x94A
The alkyl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) can have any structure as long as one or more A and/or R groups is hydrogen, hydroxy, hydroxyalkyl group, such as methoxy, ethoxy, propoxy, and aryloxy group, acyloxy group, and mixtures thereof. Thus, each R group preferably can be alkyl, aryl, hydroxy, or hydroxyalkyl group, and mixtures thereof; preferably the nonreactive R group is methyl. Each A group which blocks the ends of the silicone chain can be hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, or aryloxy group, acyloxy group, and mixtures thereof; preferably the nonreactive R group is methyl. Suitable A groups include hydrogen, methyl, methoxy, ethoxy, hydroxy, and propoxy. q is preferably an integer from about 7 to about 8,000. An example of commercially available silicones of this class is General Electric 176-12669 aqueous emulsion which comprises about 30% to about 60% of a curable silicone having Sixe2x80x94OH reactive groups, and emulsified by a mixture of cationic and nonionic emulsifiers.
Preferably, curable silicones of the present invention comprise cationic aminofunctional groups or polyalkyleneoxy groups, more preferably comprising both cationic aminofunctional groups and polyalkyleneoxy groups.
A nonlimiting example of curable aminofunctional silicone material has the formula:
ROxe2x80x94[Si(CH3)2xe2x80x94O]xxe2x80x94{Si(OH)[(CH2)3xe2x80x94NHxe2x80x94(CH2)2xe2x80x94NH2]O}yxe2x80x94R
wherein each R is hydrogen, low molecular weight alkyl group, such as, methyl, propyl, butyl, low molecular weight acyl, such as CH3CO, and mixtures thereof, x and y are integers which depend on the molecular weight of the silicone. This material is also known as xe2x80x9camodimethiconexe2x80x9d. These aminofunctional silicones are reactive, and can further condense to form higher molecular weight polymers and/or form bonds with the fabrics, and are thus highly substantive to fabrics. Examples of this class of materials are described in U.S. Pat. No. 4,911,852 issued Mar. 27, 1990 to Coffindaffer et al., said patent is incorporated herein by reference. A commercially available curable aminofunctional silicone is disclosed in this patent, namely, SF 1706 neat silicone, available from General Electric Company; this silicone comprises terminal reactive Sixe2x80x94OCH3 groups, and pendant xe2x80x94CH2CH2CH2NHCH2CH2NH2 cationic groups, and is available as specialty aqueous emulsion 124-7300 containing about 20% SF 1706. Another example is an aqueous General Electric SM 2658 emulsion comprising about 30% to about 60% of curable aminofunctional silicone with terminal reactive Sixe2x80x94OH groups, and pendant xe2x80x94CH2CH2CH2NHCH2CH2NH2 cationic groups, emulsified by cationic surfactants.
Preferred Enduring Hydrophilic Silicones.
Typical curable silicones, including curable amine functional silicones, are surface substantive and make the treated surface very hydrophobic. However, for normal usage, waterproofing of garments and other household fabrics such as towels is also not desirable and should be avoided. Therefore, it is desirable for fabric care to have silicone polymers as surface modifiers that keep or make the treated surface hydrophilic. Thus the present invention preferably relates to curable silicones that are surface substantive, but do not have the hydrophobicity negative. The preferred hydrophilic curable silicones of formula II of the present invention comprise poly(alkyleneoxy) D groups, and preferably said poly(ethyleneoxy) D groups are exposed on the treated surface, and not being concealed and hidden within and/or underneath the silicone coating layer, in order to provide the surface hydrophilicity. This is achieved by (a) having the poly(ethyleneoxy) groups capped with a C1-C4 alkyl group, a hindered alcohol group, or a protected alcohol group, to prevent the poly(ethyleneoxy) groups from reacting with the reactive Sixe2x80x94A groups to become part of the backbone and/or cross-linking groups, and (b) not having the poly(ethyleneoxy) groups capped with cationic E groups if the poly(ethyleneoxy) groups are short, since cationic E groups are believed to have the tendency to anchor deep on the treated surface and thus also driving the poly(ethyleneoxy) groups deep underneath the silicone coating layer. To effectively avoid or reduce the crosslinking by the poly(alkyleneoxy) D groups, any capping alcohol group needs to have the OH group well protected; therefore tertiary alcohol groups such as xe2x80x94CH2C(R2)OH or hindered secondary alcohol groups, such as xe2x80x94CH2CH(R4)(OH), with R4 not being H or CH3, are preferred.
However, it will be appreciated that large poly(ethylene oxide) groups are less needful of these capping group restrictions, since they are less likely to be completely covered by the silicone segments in the cured layer. Thus, the present invention also relates to hydrophilic curable silicones with uncapped pendant poly(alkyleneoxy) D groups (i.e., poly(alkyleneoxy) D groups terminated by a xe2x80x94OH) and/or capped with cationic E groups to increase crosslinking and/or surface substantivity, wherein each pendant poly(alkyleneoxy) D group preferably comprises at least about 11 ethyleneoxy units (i.e., c being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and even more preferably at least about 30 ethyleneoxy units (c being equal or greater than about 30). Similarly, when internal poly(ethyleneoxy) G groups which form part of the polymer backbone are desirable, each G group should preferably comprise at least about 11 ethyleneoxy units (i.e., v being equal or greater than 11), more preferably at least about 15 ethyleneoxy units (v being equal or greater than 15), and more preferably at least about 30 ethyleneoxy units (v being equal or greater than 30).
The present invention also preferably relates to noncurable aminofunctional silicones of formula I that comprise hydrophilic poly(alkyleneoxy) D groups. These noncurable cationic silicone polymers can provide an intermediate durability benefit which is preferred in some applications. Said noncurable cationic silicone polymers comprise poly(ethyleneoxy) D pendant and/or terminal groups that are exposed on the treated surface, and not being concealed and hidden within and/or underneath the silicone coating layer, in order to provide the surface hydrophilicity. This is achieved by (a) having the poly(ethyleneoxy) pendant groups not capped with cationic functional capping groups, (b) when cationic functional groups are needed on the poly(ethyleneoxy) pendant groups, e.g., for improved surface substantivity, each pendant poly(alkyleneoxy) D group should comprise at least about 11 ethyleneoxy units (i.e., c being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and even more preferably at least about 30 ethyleneoxy units (c being equal or greater than about 30), and/or (c) when internal poly(ethyleneoxy) G groups which form part of the polymer backbone are present, each G group should preferably comprise at least about 11 ethyleneoxy units (i.e., v being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (v being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and even more preferably at least about 30 ethyleneoxy units (v being equal or greater than 30).
Reactive, Curable Silicones Comprising Polyalkyleneoxy Groups, but not Cationic Amino Functional Groups.
Reactive, curable silicone polymers comprising polyalkyleneoxy groups, but not cationic amino functional groups are also useful in the compositions of the present invention. Said silicone polymers have the following general structure III:
(R1)aR3-aSixe2x80x94(xe2x80x94Oxe2x80x94SiR2)mxe2x80x94(xe2x80x94Oxe2x80x94SiRA)nxe2x80x94(xe2x80x94Oxe2x80x94SiRD)qxe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94Jxe2x80x94SiR2]rxe2x80x94Oxe2x80x94Si(R1)bR3-bxe2x80x83xe2x80x83(III)
These silicones are similar to those having structure II hereinabove, except that they do not comprise cationic E groups. Again in this case, the pendant and/or internal poly(ethyleneoxy) D groups should be long enough, preferably comprises at least about 11 ethyleneoxy units (i.e., c being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and even more preferably at least about 30 ethyleneoxy units (c being equal or greater than about 30); and/or the pendant and/or internal poly(ethyleneoxy) D groups should be capped with a C1-C4 alkyl group, a hindered alcohol group, or a protected alcohol group, to prevent the poly(ethyleneoxy) groups from reacting with the reactive Sixe2x80x94A groups; and mixtures thereof.
A nonlimiting example of reactive silicones of this class is the water soluble Silwet(copyright) L-720 polyalkyleneoxylated silicones with terminal reactive Sixe2x80x94Oxe2x80x94R1 groups, and butyl-capped polyethyleneoxy/polypropyleneoxy block copolymer pendant groups, with about equal number of ethyleneoxy and propyleneoxy units, and with an average molecular weight of about 12,000, and is available from CK Witco, Greenwich, Conn.